Disazo-dyestuffs



2,807,609 Patented Sept. 24, 1957 DISAZO-DYESTUFFS Jacob Danuser, Arlesheim, and Hans-Lnzi Schncan, Bettingen, Switzerland, assignors to Ciba Limited, Basel, Switzerland, :1 Swiss firm No Drawing. Application December 12, 1955, Serial No. 552,291

Claims priority, application Switzerland September 29, 1953 6 Claims. (Cl. 260-176) and CmHnrmC ONH NHCOCH=CCH:

in which m and n are whole numbers of a maximum of 2. Thus, for example very valuable disazo dyestuffs are obtained from 1 acetoacetylamino 2,5 dimethoxy 4- acetylaminobenzene and l-acctoacetylamino-2-chloro-4- acetylamino-S-methoxybenzene.

The tetrazotization of the diaminodiphenyl compounds can take place in the conventional manner, advantageously by means of hydrochloric acid and alkali nitrite. It is to be recommended as a rule to filter the solutions of the tetrazo compounds from any insoluble impurities.

The coupling of the resulting tetrazo compounds with the azo components of the specified type can take place, if desired, upon a substratum, for example, upon celin which R1CO- represents the radical of a low molecular aliphatic carboxylic acid, R2 represents a low molecular alkyl group, X represents a member selected from the group consisting of a halogen and a low molecular alkoxy group, and U represents a member selected from the group consisting of a halogen atom, a methyl group and a low molecular alkoxy group. These disazo-dyestuffs are obtained according to the invention by coupling tetrazotized 4:4'-diaminodiphenyl compounds of the formula on both sides with azo components of the formula in which formula X, RrCO, R2 and U have the meaning given above.

The tetrazo compounds of the diamines of the Formula 2 are coupled on both sides with azo components of the Formula 3, the coupling of both diazotized amino groups being advantageously with the same azo components. The low molecular alkoxy groups present in the azo components can be, for example, ethoxy groups or advantageously methoxy groups. The halogen atoms present as further substituents in the azo components can be bromine or preferably chlorine atoms.

The azo components correspond advantageously to one of the formulae (4) O C "Ham (SC im lulosic materials, impregnated with azo components of the Formula 3. However, this coupling takes place with especial advantage in substance. In the latter case, the coupling is advantageously carried out in a weakly acid, for example acetic acid medium, it being in general of value to add a wetting or dispersing agent to the coupling mixture. For this purpose wetting and dispersing agents of both ionogenic and non-ionogenic type can be used. As a dispersing agent of ionogenic type, Turkey red oil can, for example, be used, and as dispersing agents of non-ionogenic type there may be mentioned polyglycol ethers or high molecular fatty alcohols.

The new disazo-dyestuiis of the above Formula 1, when produced in substance, are valuable pigments and as a rule are distinguished by very good fastness to light, good fastness to migration (bleeding out) and in addition by temperature stability and stability to solvents. This is of value, for example, for the so-called pigment printing, i. e. for printing processes which depend upon fixing pigments by means of suitable adhesives such as casein, hardenable artificial resins, especially ureaor melamineformaldehyde condensation products, polyvinyl chloride or polyvinyl acetate solutions or emusions, or other emulsions (for example oil-in-water or water-in-oil emulsions) upon a substratum, especially upon a textile fiber or also upon other sheet material, such as paper (for example wallpaper) or glass fiber fabrics. The new pigments can also be used for other purposes, for example in finely divided form for the dyeing of artificial silk from viscose or cellulose ethers and esters or from superpolyamides or superpolyurethanes, the pigment being added to the spinning mass, or also for the manufacture of colored lacquers or lacquer base materials, solutions and products from acetylcellulose, nitrocellulose, natural resins or artificial resins, such as polymerisation or condensation resins, for example aminoplasts, phenoplasts, polyvinyl chloride, polystyrene, polyethylene, polyacryl, rubber, casein, silicone and silicone resins, the pigments being eminently suited to these purposes. They can also be used with advantage for the manufacture of colored pencils, cosmetic preparations or sheets for lamination purposes.

The new dyestuffs can normally be incorporated easily into masses or preparations of the specified types and this incorporation is advantageously effected at a stage before Example 3 these masses or preparations have assumed their final form. The necessary shaping operations, such as spinning, pressing, hardening, casting, lamination and so on can also be carried out in the presence of the pigments concerned without detriment to any necessary subsequent chemical reaction of the substratum, such as further polymerisation or condensation.

The following examples illustrate the invention, the parts being by weight unless otherwise stated and the relation between part by weight and part by volume being the same as that between the kilogram and the liter:

A mixture is prepared from 276 parts of the diazoamino compound from tetrazo- 5 tized 3:3-dichloro-4:4'-diaminodiphenyl and methyl-taurin prepared in the usual manner 300 parts of acetoacetyl-amino-2-chloro-4-acetylamino- S-methoxybenzene parts of sodium butyluaphthalene sulfonate 10 414 parts of sodium chloride or urea 1000 parts By means of this preparation fabrics of cellulosic fibers Example I can, for example, be printed as follows: From Into an acetic acid suspension of 61.2 parts of l-acetoacetylamino-2-chloro-4-acetylamino-S-methoxybenzene to 50 Parts of the Pmmng Preparatlon which a dispersing agent, for example Turkey red oil, has 30 Parts of Turkey Ted been added, there is run a solution of 25.3 parts of tetrazo- 290 Parts of tized 3:3'-dichloro-4:4-diaminodiphenyl. By addition of 30 Parts of a Sodwm hYdmXlde 801mm of 30 Percent sodium acetate, the pH value of the coupling liquid is strength adjusted to 4.5 to 5, and the temperature is allowed to 600 Parts of a neutral thlckemng 1111mm: of starch and rise to 20 C. whereby the dyestuif formation is soon tragacamh completed. Then the whole is filtered with suction and 1000 parts the pigment thoroughly washed with warm water and dried. The dyestuff gives, for example in pigment printa Prmtlng Paste p pf f 0f f fi 01' '6- ing, an orange of very good fastness properties, especi ll generated cellulose is printed w th th1s paste in the us ual f excellent bi i to solvents. manner, for example roller printing or screen printing.

By using instead f 3; 3' di h1 4;4' di i i l The printed material is then dried, steamed for five minutes 21.2 parts of 3:3'-dimethyl-4:4-diaminodiphenyl or 24.4 in the presence of an d. or example formic acld and parts of 3:3'-dimethoxy-4:4-diaminodiphenyl, an orange 9 F E the boil as usual Golflfifl Orange Priming is obtained of which the color tint is displaced more toslgfls having good fasmess P p are Obtained. wards red but which has similar properties primarily suit- Example 4 t t' l f able for plgmen pnn mg and the co ormg 0 lacquers 65 parts of polyvinyl chloride, parts of dioctylphtha- Example 2 35 late and 0.5 part of the dyestuff obtainable according to A tetrazo solution from 21.2 parts of 3:3'-dirnethyl- Example 1 are stirred together and the mixture obtained 4:4'-diaminodiphenyl is run under the surface of an acetic is thereupon passed to and fro for about 3 minutes at acid suspension of 60.3 parts of l-acetoacetylamino-ZzS- 140 to 145 C. between the two rolls of a calender. A dimethoxy-4-acetylaminobenzene. At the same time as yellow colored foil is obtained of strong color tint, very the introduction of the tetrazo solution, an aqueous solugood fastness to light and good fastness to migration. tion of a dispersing agent, for example oleolyl polyglycol What is claimed is: ether, is run into the reaction mixture. The temperature 1. A disazo-dyestuif which is free from water solubilizis maintained at 0-5 C. After the introduction of the ing groups and corresponds to the formula U U MOO-NHQ-NEb-CQ /GO-NH NH X ON==N N=NC d 0 R,

GHQ-C \OCH| tetrazo solution, the pH value of the coupling suspension in which R1CO- represents the radical of a low molecuis adjusted to 4:5 to 5 and the whole is slowly heated to lar aliphatic carboxylic acid, R2 represents a low mo- 30 0. whereby the dyestuff formation is completed. The lecular alkyl group, X represents a member selected from pigment, isolated as in Example 1, when ground in a the group consisting of a chlorine and a low molecular plasticizer, for example dioctyl phthalate, gives a fine alkoxy group, and U represents a member selected from paste which colors polyvinyl chloride foils in orange the group consisting of a chlorine atom, a methyl group tints of good fastness to light. and a low molecular alkoxy group.

By using instead of 3 :3'-dimethy1-4:4'-diaminodiphenyl 2. A disazo-dyestufl of the formula OCn Hl n In-H 0 0 ll U U l mas-CONE NH -NH OONHO-Hnni c H O-N=N N=N-C\ O H n n+1 CEh c/ \O CH' Is an 25.3 parts of 3:3dichloro-4:4'-diaminodiphenyl and in which U represents a member selected from the group proceeding otherwise as described in the above example, consisting of a chlorine atom, a methoxy and a methyl a yellow dyestufi is obtained of similar properties. group, m and n are whole numbers of at the most 2.

6 3. A disazo-dyestufi of the formula 0 CnHzn O CnHInM 0 0 1% U U l CmHmM-lc ONE NH NH CONEO-Hz-m I /CN=N N=NO\ 1 CHr-O o0H= in which U represents a member selected from the group consisting of a chlorine atom, a methoxy and a methyl group, m and n are whole numbers of at the most 2.

4. The disazo-dyestuff of the formula 11,co 0-011, I! 0 mc-oc-m NHG\ J-HN NH--C 0-4311 o--N=N N=N-C- 4 mO-O H m o-cH, 6H on H3) 5. The disazo-dyestufl of the formula Ego-0 0-0 H; o o H|0-0OHN NH-i') /PJHN NH-O 0-011, c-N=N N=N-G 1 1 HaO-O I 1 C-QHI H H 6. The disazo-dyestufi of the formula rho-0 0-011, 0 0 oar-o O-HN NH!2\ /H7HN NH-C 0-011.

0N==N N=N-O Om HaC-C C-OHI l 1 o 0 5| H E References Cited in the file of this patent UNITED STATES PATENTS 1,932,577 Eichwede et a1. Oct. 31, 1933 2,361,566 Reynolds Oct. 31, 1944 2,361,567 Reynolds Oct. 31, 1944 2,739,146 Weigele et a1. Mar. 20, 1956 

1. A DISAZO-DYESTUFF WHICH IS FREE FROM WATER SOLUBILLIZING GROUPS AND CORRESPONDS TO THE FORMULA 